JPH08245362A - External agent for preventing ultraviolet damage - Google Patents

Abstract

PURPOSE: To obtain the subject agent having greatly improved preventing effect against skin damage based not only on the effect to lower the mount of the ultraviolet arriving on the skin but also on the effect to prevent skin damage by caused ultraviolet and that to recover the skin from the damage. CONSTITUTION: This external agent for preventing ultraviolet damage contains at least one kind of vitamin A selected from the group consisting of vitamin A, a vitamin A ester and an ester of a vitamin-A acid as an ultraviolet protecting agent, and an active component for keeping normal skin function and recovering damaged skin. Preferably, the compounding ratio of a vitamin A is >=0.05wt.% and <=2.0wt.% based on the total amount of the agent in the objective external agent.

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to an external preparation for protection against ultraviolet damage. More specifically, by using a vitamin A and / or a vitamin A ester and / or a vitamin A acid ester having both normal skin function maintaining activity and damaged skin healing activity together with an ultraviolet protective agent, it is possible to prevent excessive sunlight exposure. The present invention relates to an external preparation for protecting against UV damage that effectively protects the skin from skin disorders.

[0002]

2. Description of the Related Art As is well known, at the present time when the destruction of the ozone layer, which protects the organisms on the earth from excessive UV exposure, is progressing, the damage caused by the ultraviolet rays of sunlight, particularly the adverse effects on the skin, such as the skin There is an ever increasing need to protect humans from skin damage, accelerated skin aging, and increased incidence of skin cancer. In fact, the incidence of squamous cell carcinoma in Australia and the United States is already higher than that of rectal cancer, lung cancer and breast cancer, and the association between sunlight and skin cancer cannot be ruled out (Nature, 372; 773-776 (1994)). ).

Therefore, various ultraviolet protective agents have been developed for the purpose of reducing the amount of ultraviolet rays reaching the skin by absorbing or blocking ultraviolet rays, and based on these various ultraviolet protective agents have been developed. Screen products are commercially available. This different level of protection is displayed as a number called the Sun Protection Factor (SPF).

However, there are problems to be improved in these sunscreen products. That is, the conventional sunscreen product can protect the skin damage caused by UV exposure to some extent by its UV protection effect, but its protection effect has not yet reached a satisfactory level.

In particular, once the skin is damaged by exposure to ultraviolet rays, resistance to ultraviolet rays at the damaged site is extremely reduced as compared with that at a normal site, and deterioration of the damage is accelerated. Therefore, a large number of sunscreen agents are often used frequently, which causes pollution of seawater, pools and the like, and also causes environmental pollution.

Further, the use of a large amount of the UV protection agent is not always preferable for the health of the user.

[0007]

There is increasing social interest in effectively protecting the skin from the harmful effects of excessive ultraviolet rays in sunlight, and it is more effective and safer than ever before for external use for protection against ultraviolet damage. The development of agents is desired.
For that purpose, it is necessary to create an external preparation having the following functions [A] and [B] at the same time.

[A] The amount of ultraviolet rays reaching the skin is reduced. [B] The normal skin function is enhanced, the resistance to ultraviolet rays is enhanced, and at the same time, the damaged skin is quickly repaired, and further deterioration of the damaged site weakened by ultraviolet rays is suppressed as much as possible.

As described above, the problem [A] has been solved to some extent in the conventional sunscreen agent, but the importance of the problem B has been overlooked.
The effective and safe external preparation for UV protection has not been developed.

By satisfying not only the problem [A] but also the problem [B] at the same time, the effect of protecting the skin from excessive ultraviolet rays in sunlight is further improved.

Items to be considered in order to solve the problem [B] are listed below. It is necessary to have both normal skin function maintenance activity and damaged skin recovery activity. Normal skin function maintenance activity and damaged skin recovery active ingredient are
It is necessary that the ingredient has a strong effect of maintaining the normal skin function and an effect of recovering the damage and is excellent in safety.

That is, steroids and the like having a strong damage-recovering effect and the like but strong side effects are not preferable as the damaged skin-recovering active ingredient used in the present invention. Conversely, placental extracts, elastin, etc., which have few side effects but have relatively weak damage recovery effects, etc., are not appropriate as damaged skin recovery active ingredients used in the present invention.

The active ingredient for maintaining normal skin damage function and the active ingredient for repairing damaged skin must be relatively inexpensive ingredients. That is, even if the ingredients satisfy the above conditions (1) and (2), if the ingredient is too expensive, the versatility of the external preparation finally provided is reduced, which is not preferable.

That is, the problem to be solved by the present invention is to satisfy the above-mentioned problem [A] in order to reduce the amount of ultraviolet rays reaching the skin and at the same time have the effect of preventing the skin damage and the effect of recovering the damaged skin by the ultraviolet rays. UV protectant to
It is an object of the present invention to provide a highly effective external preparation for protecting against UV damage, which contains a component having normal skin function maintenance activity and damaged skin recovery activity satisfying the problems [B] to.

[0015]

Means for Solving the Problems The inventors of the present invention have made extensive studies to solve the above problems. As a result, the present invention can be obtained by using vitamin A and / or vitamin A ester and / or vitamin A acid ester as components satisfying the above problems [B] to, in addition to the components satisfying the above problems [A]. It came to completion.

That is, the present invention provides a vitamin A, a vitamin A ester and a vitamin A as an ultraviolet protective agent, a normal skin function maintaining active ingredient and a damaged skin restoring active ingredient.
Provided is an external preparation for protecting against ultraviolet damage, which comprises one or more vitamins A selected from the group consisting of acid esters.

The present invention will be described in detail below. First, the vitamin A, ie, vitamin A, vitamin A ester and vitamin A acid ester as the active ingredient for maintaining normal skin function and the active ingredient for recovering damaged skin in the present invention will be described. In the present invention, Vitamin A means all-trans-retinol, Vitamin A ester means the ester of Vitamin A and carboxylic acid,
The vitamin A acid means all-trans-retinoic acid, and the vitamin A acid ester means an ester of the vitamin A acid and a hydroxy compound. Typical vitamin A esters include, for example, retinyl acetate,
As typical vitamin A acid ester such as retinyl palmitate, for example, ethyl retinoate, butyl retinoate and the like can be mentioned, and these vitamin A ester and vitamin A acid ester can be applied to the present invention. The ester is not limited. Generally, the vitamin A ester and the vitamin A acid ester are superior in stability to vitamin A, and are preferable for application of the present invention. Further, among vitamin A esters, retinyl acetate is preferable because it is available at low cost.

Vitamin A and vitamin A ester (hereinafter referred to as vitamin A, etc.) are known as components having an excellent function of maintaining normal skin function and a function of recovering damaged skin (Vitamin Handbook, edited by Japan Vitamin Society). , Fat-soluble vitamins, p.11 (1989), Kagaku Dojin Co., Ltd .; Blomhoff, R.ed., Vitamin A in health and disea
se, p.365 (1994)), it has good permeability to skin cells because it is fat-soluble. That is, vitamin A and the like are excellent components in terms of their effectiveness in providing an external preparation having desired effects.

Vitamin A and the like are also approved as oral preparations and intramuscular injections, and in such a dosage form, when an extremely large amount of long-term administration is performed, anorexia, headache, and other excessive symptoms occur. Have been reported (Kihachiro Shimizu, Kenji Fukumuro, Diseases and Remedies, p.370 (1992))
, Nankodo Co., Ltd.). When it is used as an external preparation as in the present invention, side effects of vitamin A and the like do not pose any problem, and vitamin A and the like are excellent in safety. Furthermore, vitamin A and the like are also excellent in that they can be easily obtained at low cost.

As described above, the vitamin A and the like used in the present invention are excellent components which can satisfy the conditions of the problems [B] to mentioned above in the "problems to be solved by the invention".

It should be noted that vitamin A and the like are converted into retinoic acid through retinol in skin cells, and the physiological action of vitamin A and the like is based on retinoic acid. However, since retinoic acid has strong side effects and does not satisfy the condition of the problem [B], it is unsuitable as a compounding ingredient in the external preparation for UV damage protection of the present invention. In addition, various synthetic retinoids having retinoic acid-like activity are known, but these are also unfavorable from the viewpoint of safety because they have strong side effects (pharmacology and treatment, 10: 5033-5044 (198
2)). On the other hand, retinoic acid ester has weak side effects and is a component satisfying the problems [B] to
It can be used in the same manner as the above vitamin A and the like.

Further, retinal, which is positioned as an intermediate when retinol is converted into retinoic acid in skin cells, is not only an unstable substance but also has a high production cost, and the external preparation for UV damage protection of the present invention. It is not preferable to use it as a compounding ingredient.

The compounding ratio of vitamin A or the like and / or vitamin A acid ester in the external preparation for UV damage protection of the present invention is preferably at least 0.05% by weight of the total external preparation, and the upper limit is particularly limited. However, considering the effectiveness and economical efficiency of the external preparation for UV damage protection of the present invention, it is preferable to mix it in a ratio of about 2.0% by weight at the maximum.

Next, the UV protective agent in the external preparation for protecting UV damage of the present invention will be described. The "ultraviolet protection agent" used in the present invention is both a "ultraviolet blocking agent" which is a substance that scatters and reflects ultraviolet rays by a physical action, and a "ultraviolet absorber" which is a substance that physically absorbs ultraviolet rays. Is meant.

Examples of the ultraviolet blocking agent applicable to the external preparation for protecting ultraviolet damage of the present invention include fine particle powders of metal oxides such as titanium oxide, zinc oxide, iron oxide and tin oxide. It is not limited.

Further, as the ultraviolet absorber applicable to the external preparation for protecting ultraviolet damage of the present invention, para-aminobenzoic acid (PABA), glyceryl para-aminobenzoate, 4
-Ethyl bis (hydroxypropyl) aminobenzoate,
PABAs such as octyl paradimethylaminobenzoate and its derivatives; benzyl salicylate, octyl salicylate,
Salicylic acid derivatives such as homomenthyl salicylate, triethanolamine salicylate, potassium salicylate, amyl salicylate, para-isopropylphenyl salicylate, isopropylbenzyl salicylate; benzyl cinnamate,
2-Methylhexyl paramethoxycinnamate, potassium cinnamate, octyl cinnamate, ethyl 4-isopropyl cinnamate, ethyl 2,4-isopropyl cinnamate, 2,4
-Methyl isopropyl cinnamate, potassium paramethoxycinnamate, sodium paramethoxycinnamate, diethanolamine paramethoxycinnamate, propyl paramethoxycinnamate, isopropyl paramethoxycinnamate, isoamyl paramethoxycinnamate, para Octyl methoxycinnamate, 2-ethoxyethyl paramethoxycinnamate, cyclohexyl paramethoxycinnamate, α-cyano-β-
Cinnamic acid derivatives such as ethyl phenylcinnamate, ethylhexyl α-cyano-β-phenylcinnamate, and hexyl α-cyanoparamethoxycinnamate; oxybenzone, dioxybenzone, thrisobenzone, mexenone, 4-phenylbenzophenone-2- Benzophenone derivatives such as 2-ethylhexyl carboxylate; Anthranilic acid derivatives such as 2-acetylanthranilic acid homomenthyl and anthranilate menthyl; 1- (tert-Butylphenyl-3
(4-methoxyphenyl) propane-1,3-dione,
Dibenzoylmethane derivatives such as 1-p-cumenyl-3-phenylpropane-1,3-dione and 1,3-bis (4-methoxyphenyl) propane-1,3-dione; α-
(2-Oxobone-3-ylidene) paraxylene-2
-Sulfonic acid, α- (2-oxobone-3-ylidene) toluene-2-sulfonic acid, 3- (4-methylbenzylidene) bornan-2-one, 3-benzylidenebornan-2-one, N, N, N-trimethyl-4- (2-
Oxobone-3-ylidenemethyl) anilium methylsulfate, 5- (3,3-dimethyl-2-norborinidene)
Camphor derivatives such as 3-penten-2-one; Others: digalloyl trioleate, lawson and dihydroxyacetone, 2-phenylbenzimidazole-5-sulfonic acid, urocanic acid, 5-methyl-2-methylbenzoxazole, 3, Examples thereof include sodium 4-dimethoxyphenylglyoxylate, 2- (2hydroxy-5-methylphenyl) benzotriazole and dibenzalazine, but are not limited thereto.

Among these ultraviolet absorbers, PA
BA and its derivatives, salicylic acid derivatives, paramethoxycinnamic acid derivatives, 4-methoxybenzophenone derivatives and the like are preferably applied to the present invention from the viewpoint of safety, economy and the like.

The above-mentioned UV protective agents can be blended alone in the external preparation for UV damage protection of the present invention, but can also be used in an appropriate combination. Furthermore, the preparation of the external preparation for protecting ultraviolet damage of the present invention will be described.

The present invention can be applied to all dosage forms which are considered to be effective in imparting the UV damage protection ability, such as creams, lotions, oils, gels, sticks and mousses. is there. The external preparations for protecting the ultraviolet damage of the present invention in these dosage forms are used as a mixture with vitamin A and / or vitamin A acid ester and a cosmetically acceptable cosmetic base with the ultraviolet protector. In the test examples and formulation examples described below, specific embodiments of the external preparation for UV damage protection of the present invention are illustrated.

It is widely known that vitamin A and the like have excellent normal skin function maintenance activity and damaged skin recovery activity. However, it cannot be said that this effective activity of vitamin A and the like is fully utilized for maintaining and promoting human health. Certainly, an external preparation containing vitamin A or the like has been proposed (JP-A-1-93516).
JP-A No. 3-118312, JP-A No. 61-
No. 40210), but these are focused on being useful for beauty.

Further, an external preparation containing a vitamin A acid ester has been proposed as a skin ulcer treatment agent, a digestive tract ulcer treatment agent, and an antitumor agent (JP-A-4-244058 and JP-A-4-244076). Gazette).

Further, an example for stabilizing vitamin A using an ultraviolet absorber has been proposed (International Publication WO94 / 01074).

However, in order to establish a method for safely and effectively protecting human skin from damages caused by excessive ultraviolet rays caused by sunlight, which have become more and more social issues in recent years, The synergistic preventive and protective effect of the combined use of vitamin A etc. and / or vitamin A acid ester and an ultraviolet protective agent is not positively taken into consideration.

The present invention provides a unique technique which is far superior to the prior art with respect to the effect of preventing and protecting the skin from the adverse effects of UV irradiation by sunlight.

[0035]

EXAMPLES Test examples and formulation examples are described below as examples, but the technical scope of the present invention is not limited by these examples and should not be construed.

[Test Example] In the formulations shown in Table 1 below, an external preparation (Example 1 and Comparative Example 1) in which retinyl acetate was added to an ultraviolet protection agent and Comparative Example 2 in which retinyl acetate was not added are shown. A prescription external preparation was manufactured.

[0037]

[Table 1] Table 1

<Test for Protective Effect on Skin Damage Induced by Exposure to Solar UV Light> (Test Method) A practical use test at the beach was conducted. The first
After applying the three kinds of samples shown in the table to 20 people every day on the back of each person divided into 3 equal parts, and after performing the treatment for exposing the skin for 4 hours at the seaside in the summer for 1 week. A test test for the protective effect against skin disorders was conducted. The results are shown in Table 2.

Table 2 Evaluation criteria for skin disorders: Blisters were observed (■), no blisters were observed (□) Scratching was observed (▲), Scratching was not observed (△) Erythema was observed ( ●), no erythema was observed (○)

UV protector (2,2'-dihydroxy-
4-Methoxybenzophenone) and retinyl acetate were added to the external preparation of the present invention (Example 1) in which 0.5% by weight of the total external preparation was applied, and 3 out of 20 subjects had slight erythema. It was only admitted. On the other hand, with the external preparation of Comparative Example 2 containing no retinyl acetate at all, erythema was observed in 18 out of 20, of which 14 were even more sensitive and blisters were observed in 4 of them. Further, in the external preparation of Comparative Example 1 in which retinyl acetate was blended in an amount of 0.01% by weight based on the total amount of external preparation, erythema was observed in 18 subjects, tingling in 11 subjects, and blisters in 3 subjects.

From these results, the external preparation of the present invention containing 0.5% by weight of retinyl acetate as an ultraviolet protective agent with respect to the total external preparation has a skin disorder as compared with the external preparation containing only the ultraviolet protective agent. It became clear that the defense effect of was extremely high. Further, when the compounding ratio of retinyl acetate was 0.01% by weight based on the whole external preparation, the skin damage protecting effect was insufficient.

The formulation examples of the external preparation of the present invention will be described below as formulation examples. Each of the external preparations showed an excellent protective effect against skin damage induced by exposure to sunlight and ultraviolet rays.

Formulation Example 1 Cream wt% Oil phase Octyl dimethylaminobenzoate 8.0 Oxybenzone 5.0 Octyl methoxycinnamate 6.0 Retinyl palmitate 1.0 Cyclic silicone 10.0 Self-emulsifying mono Glycerin stearate 5.0 Polyethylene glycol (40E.O) monostearate 2.0 Cetyl alcohol 1.0 Octyl palmitate 10.0 Perfume 0.1 Water phase glycerin 5.0 Paramethoxycinnamic acid diethanolamine 8.0 Titanium oxide 3.0 Xanthan gum 0.2 Hydroxyethyl cellulose 0.1 Preservative Appropriate amount Purified water Residual amount (Production method) The oil phase part and the water phase part are each heated to 70 ° C.,
After completely dissolving, the oil phase was added to the aqueous phase and emulsified with an emulsifier. The emulsion was cooled using a heat exchanger to obtain a cream.

[Formulation Example 2] Lotion% by weight Oil phase Octyl dimethyl parabenzoaminobenzoate 7.0 Oxybenzone 3.0 Retinyl acetate 0.5 Triethanolamine stearate 4.0 Liquid paraffin 10.0 Polyoxyethylene myristic acid Myristyl ether 4.0 (3E.O.) aqueous phase carboxyvinyl polymer (Carbopol 1342) 0.2 propylene glycol 5.0 triethanolamine 0.7 preservative proper amount purified water residual amount (production method) Heating the water phase part to 70 ° C,
After completely dissolving, the oil phase was added to the aqueous phase and emulsified with an emulsifier. This emulsion was cooled using a heat exchanger to obtain a lotion.

Formulation Example 3 Oil wt% Octyl paramethoxycinnamate 4.0 Ethyl retinoate 0.1 Lauryl lactate 15.0 Liquid paraffin 35.0 Isocetyl alcohol 10.0 Perfume 0.05 Octyl palmitate Residue Amount (Production Method) The above components were mixed, heated to 70 ° C., completely dissolved, and then cooled using a heat exchanger to obtain an oil.

[Formulation Example 4] Gel wt% aqueous phase carboxyvinyl polymer (Carbopol 940) 0.75 triethanolamine 0.75 purified water balance alcohol phase retinyl acetate 0.05 para-hydroxypropylamino ethyl benzoate 4 0.0 Ethanol 15.0 Propylene glycol 22.0 Others Polyoxyethylenesorbitan monolaurate 0.5 (20E.O) Perfume Appropriate amount Preservative Appropriate amount (Production method) Water phase component and alcohol phase component are mixed respectively, and then This mixture was emulsified by adding polyoxyethylene sorbitan monolaurate (emulsifier) and an appropriate amount of fragrance. Furthermore, a preservative was added thereto to prepare a gel.

Formulation Example 5 Lip Palm Stick Weight% Octyl paradimethylaminobenzoate 7.0 Oxybenzone 3.0 Retinyl palmitate 0.4 Castor oil Appropriate amount octyl dodecanol 5.0 Beeswax 15.0 Ozokerite 6. 0 myristyl lactate 4.0 candelilla wax 6.0 vaseline 5.0 fragrance suitable amount (manufacturing method) After the above ingredients are completely dissolved by heating to 70 ° C, they are emulsified with an emulsifier and cooled using a heat exchanger. Then, a lip palm stick was prepared.

Formulation Example 6 Moose wt% Oil phase Triethanolamine stearate 5.0 Stearyl alcohol 1.5 Octyl salicylate 5.0 Oxybenzone 3.0 Octyl paramethoxycinnamate 3.0 Retinyl acetate 0.5 PVP / hexadecene copolymer 3.0 Aqueous phase hydroxyethyl cellulose 0.3 Triethanolamine 0.75 Ethanol 15.0 Preservative Appropriate amount Purified water Residual amount (manufacturing method) Oil phase part and water phase part are each at 70 ° C Heat
After completely dissolving, the oil phase was added to the aqueous phase and emulsified with an emulsifier. This emulsion was cooled using a heat exchanger to prepare a mousse stock solution. As the propellant in the mousse jet cylinder, 5.0 wt% of propellant A-46 (isobutane and propane) was used with respect to 95.0 wt% of mousse stock solution.

As described above, by mixing an appropriate amount of vitamin A or the like and / or a vitamin A acid ester with the ultraviolet protective agent, it has a drastically improved effect in protecting the skin damage caused by exposure to sunlight and ultraviolet rays. The major feature of the present invention is the successful creation of the external preparation.

[0050]

INDUSTRIAL APPLICABILITY According to the present invention, not only by the effect of reducing the amount of UV rays reaching the skin but also by the activity of preventing skin damage by UV rays and the activity of recovering damaged skin, the effect of UV damage protection is dramatically improved. An external preparation is provided.

Claims (2)

[Claims] 1. One or more vitamin A compounds selected from the group consisting of vitamin A, vitamin A ester and vitamin A acid ester as an ultraviolet protective agent, an active ingredient for maintaining normal skin function and an active ingredient for recovering damaged skin. An external preparation for protecting against UV damage, which comprises: 2. A blending ratio of one or more vitamins A selected from the group consisting of vitamin A, vitamin A ester and vitamin A acid ester, relative to the whole external preparation.
The external preparation for protecting against ultraviolet damage according to claim 1, wherein the content is 0.05% by weight or more and 2.0% by weight or less.